Blend of styrene polymers for use in floor polish compositions

ABSTRACT

A floor polish composition having excellent resistance to plasticizer migration contains water, a mixture of a styrene copolymer (styrene and acrylic or methacrylic acid) and a styrene multi-polymer (styrene, acrylic acid, an ester of acrylic acid and acrylonitrile) and suitable waxes, alkali soluble resins and surfactants.

United States Patent n 1 Gleason [4s] A r. 17 1973 [54] BLEND OF STYRENEPOLYMERS FOR [56] References Cited USE IN FLOOR POLISH COMPOSITIONSUNITED STATES PATENTS [75] I Edward Hinsaale Gleason, 3,467,610 9/1969Fiarman et al. ..260/22 n Pa. 3,457,208 7/1969 Sullivan et al....260/28.5 I i I 2,767,153 lO/l956 Sutton ..260/29.6 [73] Assignee:Sinclair-Koppers Company, Pitts- 3,502,604 3/1970 Nakatsuka et a1..260/29.6

burgh, Pa. 1 Primary Exar niner-John C. Bleutge [22] AssistantExaminer-OJ. Seccuro [2 pp 80,501 Attorney-William G. Kratz, Jr. et al IRelated US. Application Data 57] ABSTRACT [62] 23: of 1969 aban' floorpolish composition having excellent resistance to plasticizer migrationcontains water, a mixture of a 52 us. Cl ..260/898, 260/22 CB 260/27 RStyrene (Styrene and acrylic methacrylic 260/285 R 260/296 Rw 266/295acid) and a styrene multi-polymer (styrene, acrylic 2 0 30 R 2 0 332 R 26/ 73 2 0 97 acid, an ester Of acrylic acid andacrylonitrile) and B 1 /13&8 1 17/139 suitable waxes, alkali soluble resins and surfactants. [51]lnt.'Cl. ..C08f 29/56 58 Field of Search ..260/898 1 D'awmgs BACKGROUNDOF THE INVENTION Plasticizer migration is a problem encountered withfloor polish films. Most of the new hard floor coverings are made ofvinyl that is rich in plasticizers, such as dioctyl phthalate. Theplasticizer is able to migrate from the flooring into a polish film ifthe composition of the polish film has an affinity 'for the plasticizer.The occurrence of such migration causes the dirt pick-up of the polishto increase and detracts from the usefulness of the polish.

It has now been found that the use of a blend of a styrene copolymer andan especially prepared styrene multi-polymer containing controlledamounts of styrene, acrylic, or methacrylic acid, an ester of such acidand acrylonitrile results in overcoming the affinity of the polish filmfor plasticizers.

The term plasticizer migration is used herein to define the migration ofplasticizers used in floor tiles, such as vinyl tiles, into a polishfilm containing acrylate or styrene-acrylate polymers, the migrationleading to tackiness in the film that makes the film subject to dirtpick-up.

SUMMARY OF THE INVENTION Floor polish compositions containing alkalisoluble resins, waxes, surfactants and aqueous emulsion styrene polymersare made resistant to plasticizer migration by the use of a specificadmixture of styrene polymers. The polymer content of the admixtureconsists essentially of 50-80 percent by weight of: (a) a styrenecopolymer consisting of styrene and 5-10 percent acrylic or methacrylicacid and 50-20 percent by weight of: (b) a styrene multipolymerconsisting of -40 percent by weight of styrene and 90 60 percent of amixture of ethylenically unsaturated monomers of the formula:

wherein R is COOH, COOR wherein R is an alkyl group having 1-8 carbonatoms, and C E N, and R, is hydrogen or methyl. This mixture ofethylenically unsaturated monomers contains from l-lO percentby weightof said monomer where R is COOH, 30-80 percent of said monomer where Ris -COOR and 10-25 percent of said monomer where R is -C E N, based onthe multi-polymer.

DETAILED DESCRIPTION The floor polish composition contains a specificratio of a styrene emulsion copolymer and a specially copolymer isgenerally termed a hard polymer because of its brittle properties andalthough forming a tough film, is subject to crazing or cracking if usedalone in floor-polishes. When employed in polishes, significant amountsof plasticizers are needed to reduce the brittle character of thepolymer.

The specially prepared styrene emulsion multipolymer consists of apolymer formed from 10-40 percent styrene and -60 percent of a mixtureof ethylenically unsaturated monomers. The ethylenically unsaturatedmonomers are all of the general formula:

R1 I CH2=(|3R wherein R is -COOH; or R is COOR wherein R is an alkylgroup having 1-8 carbon atoms; or R is C E N; and R, is selected fromhydrogen and a methyl group.

In order to obtain the beneficial properties of the polish of thepresent invention, the resistance to plasticizer migration, the mixturemust have certain percentages of the various ethylenically unsaturatedmonomers. The mixture of ethylenically unsaturated monomers must containbased on the multi-polymer, from l-lO percent by weight of theethylenically unsaturated monomer wherein R is COOl-l, such as acrylicacid or methacrylic acid. From about 30-80 percent of the mixture mustbe the ethylenically unsaturated monomer wherein R is COOR with R beingan alkyl group of from l-8 carbon atoms, such as ethyl acrylate,Z-ethylhexyl acrylate, butyl acrylate, ethyl methacrylate and the like.The remaining monomer, acrylonitrile or methacrylonitrile must bepresent in about 5-25 percent.

The emulsion polymers are readily prepared from the desired monomers byconventional aqueous emulsion polymerization procedures. Preferably, themonomers are premixed, the catalyst is premixed to form an aqueoussolution or slurry and these two premixes added to an aqueous charge ina reactor. The catalyst premix comprises water, catalyst, dispersants,and emulsifying agents. Conventional polymerization catalysts ormixtures thereof including potassium persulfate, benzoyl peroxide,lauroyl peroxide, cumene hydroperoxide, di-tertiary-butyl peroxide,azobisisobutryonitrile and the like. The catalysts are generally used inabout 0.0ll.0 part per parts of total monomers.

Conventional emulsifying agents such as alkali metal salts of long chainalkyl sulfates and sulfonates, ethylene oxide condensates of long chainfatty acids, alcohols or mercaptans, sodium salts of sulfonatedhydrocarbons, alkyl arylsulfonates and the like are usable.Representative emulsifying agents include such compounds as sodiumlauryl sulfate, sulfosuccinic acid esters, sodium salts of bioctylsulfosuccinic acid, sodium salts of sulfonated cetyl alcohol, sodiumpyrophosphate and alkyl aryl polyether alcohol.

The polymerizations are carried out under acidic conditions and theaqueous emulsion polymer -pI-l raised to a pH of about 8-10, followingthe polymerization, with inorganic or organic bases such as sodiumhydroxide, ammonium, hydroxide, potassium hydroxide, monoethanolamine,etc. The water content of the aqueous system is generally such thatbetween about 30-55 percent solids are present during the decreased 'as'desired.

emulsion/are mixed togetherand there are added thereto plasticizers,dispersing agents or coalescing agents, an alkali soluble resin and asuitable wax emulsion, all,of which are generally known in the art. Theparticular polish components that are added to the novel blend ofstyrene polymers of the invention are up to the user. These componentsare familiar to the polish formulation art and are not critical to thepresent invention. 7

Examples of suitable alkali-soluble resins are rosin acid,maleate-modified rosin acid ester, shellac, styrene, styrene-maleicanhydride copolymers, polyesters or alkali soluble alkyds,pentaerythritol esters of rosin, manilla gum, Loba gum and the like.

Suitable waxes, which are generally added as about a -20 percent byweight aqueous emulsion, are the animal, vegetable and synthetic waxessuch as carnuba, polyethylene, polypropylene, oxidized microcrystallinewax, beeswax, montan, and the like.

In addition, about 0.5-1 percent based on the total polish compositionof a levelling or coalescing agent is added, such as tributoxyethylphosphate, triethyl phosphate, tributyl phosphate, tricresylphosphate, triphenyl phosphate, diethylene glycol monomethyl ether,diethylene glycol monoethyl ether and the like.

The invention is further illustrated by the following examples whereinparts are parts by weight unless otherwise indicated.

EXAMPLE I A styrene copolymer emulsion (Emulsion A) was prepared usingconventional procedures to produce a copolymer containing 90 partsstyrene and 10 parts acrylic acid.

A styrene multi-polymer emulsion (Emulsion B) was prepared, byconventional emulsion polymerization, having the following compositions:

Styrene 13.5 parts Ethyl Acrylate 65 parts Acrylonitrile parts AcrylicAcid 1.5 part Both copolymer emulsions were adjusted to a solids glycol;0.1 part 2-pyrolidone; 3.7 parts water and 0.4.

parts FC-128 at 1 percent solids. The polish composition had a totalsolids content of 14.9 per cent and a pH of 8.8.

50 parts Styrene Z-Ethylhexyl Acrylate 45 parts 5 parts Acrylic Acid Apolish composition was prepared similar to that of Example 1 but usingEmulsions C-and D in place of Emulsions A and B. The polish compositionhad a solids content of 13 percent and a pH of 8.9. v

EXAMPLE Ill Thev floor polish compositions of Examples 1 and II werecompared with respect to plasticizer migration. The plasticizermigration was determined by the amount of soiling on dirt pick-upevidenced by the polish when used on various substrates. Sixsubstrateswere used, including linoleum, vinyl asbestos tile, solidvinyl tile, asphalt tile, rubber tile and vinyl corlon. The applicationand test methods used to prepare the floor samples were from CSMABulletin No. 339-63. Numerical values were used to rate the results asfollows: (1) Excellent; (2) Excellent-Good; (3) Good-Excellent; (4)Good; (5) Good-Fair; (6) Fair-Good; (-7) Fair; (8) Fair-Poor; (9)Poor-Fair; (10) Poor; (1 l) Unacceptable. The results of the testing arelisted in Table 1.

TABLE I Time of Dirt Pick-Up Resistance Substrate Exposure Polish ofPolish of Example 1 Example 11 Linoleum 1 day 3 5 1 week 2 4 VinylAsbestos 1 day 3 5 1 week 5 8 Vinyl 1 day 3 8 1 week 7 10 Asphalt 1 day3 5 1 week 5 5 Rubber 1 day 3 5 1 week 3 7 Vinyl Corlon 1 day 1 5 1 week3 5 As is seen from the test results, the polish formula- I tion ofExample 1 has consistently increased dirt pickup resistance, i.e,reduced plasticizer migration, than a comparable polish having a polymerblend without the acrylonitrile content.

EXAMPLE 1V Polish formulations prepared generally according to Example 1and having the following blends of styrene copolymers and styrenemulti-polymers are also resistant to plasticizer migration:

95 parts styrene 65 parts ethyl methacrylate 8 parts acrylic acid 15parts acrylonitrile lV-4 5 parts methacrylic acid 20 parts styrene 95parts styrene 68 parts ethyl acrylate 2 parts acrylic acid partsacrylonitrile What is claimed is:

rated monocarboxylic acid selected from acrylic and methacrylic acidand;

b. said styrene multi-polymer consisting of 10-40 percent by weight ofstyrene and -60 percent by weight of a mixture of ethylenicallyunsaturated monomers of the formula:

R17 CHg=( JR wherein R is selected from -COOH;C0OR wherein R is an alkylgroup having 1-8 carbon atoms; and C EN; and R is hydrogen or methyl;said styrene multi-polymer containing 1-10 percent by weight of saidmonomer where R is -COOH, 30-80 percent of said monomer where R is -COORand 5-25 percent of said monomer where R is C E N.

